Graphene Mediates Charge Transfer between Lead Chromate and a Cobalt Cubane Cocatalyst for Photocatalytic Water Oxidation.

The interfacial barrier of charge transfer from semiconductors to cocatalysts means that the photogenerated charges cannot be fully utilized, especially for the challenging water oxidation reaction. Using cobalt cubane molecules (Co4 O4 ) as water oxidation cocatalysts, we rationally assembled partially oxidized graphene (pGO), acting as a charge-transfer mediator, on the hole-accumulating {-101} facets of lead chromate (PbCrO4 ) crystal. The assembled pGO enables preferable immobilization of Co4 O4 molecules on the {-101} facets of the PbCrO4 crystal, which is favorable for the photogenerated holes transferring from PbCrO4 to Co4 O4 molecules. The surface charge-transfer efficiency of PbCrO4 was boosted by selective assembly of pGO between PbCrO4 and Co4 O4 molecules. An apparent quantum efficiency for photocatalytic water oxidation on the Co4 O4 /pGO/PbCrO4 photocatalyst exceeded 10 % at 500 nm. This strategy of rationally assembling charge-transfer mediator provides a feasible method for acceleration of charge transfer and utilization in semiconductor photocatalysis.

Identifying and Removing the Interfacial States in Metal-Oxide-Semiconductor Schottky Si Photoanodes for the Highest Fill Factor.

A critical bottleneck for realizing an efficient Schottky type Si photoelectrode is minimizing the charge extraction losses across the heterointerface via reducing the unfavorite defects. This requires a clear microscopic insight into the correlation between interfacial features and photoconversion. Herein, by taking the n-Si/oxide (MOx)/Ni as the prototype, the heterointerface with the different characteristics and its effects on charge transportation and the corresponding photoelectric/photoelectrochemical (PEC) behaviors were clarified. An ultra-thin AlOx layer can effectively diminish the interfacial pinning of n-Si/Ni and significantly facilitate the photoconversion; meanwhile, it results in some unexpected donor-like deep defects at around 0.59 eV below the conduction band of n-Si, which could be ionized under a reverse bias and cause about 10% photogenerated charge recombination. Fortunately, these deep defects can be further eliminated by cooperating AlOx with a thin Au layer. The AlOx/Au dual-interlayer can remove almost all unexpected defects and maximize the efficiency of the electric field for charge extraction from semiconductor Si for the surface catalytic reaction. Eventually, the n-Si/SiOx/AlOx/Au/Ni/NiFeOx photoanode exhibited a record fill factor of 0.75 for the corresponding photoelectric device and an applied bias photon-to-current efficiency of 3.71% for PEC water oxidation. This study provides definite insights into interfacial electronic states and elaborates their crucial role in solar photoelectric conversion.

Enhancement of Plasmon-Induced Photoelectrocatalytic Water Oxidation over Au/TiO2 with Lithium Intercalation.

Plasmon-induced chemical reaction is an emerging field but its development faces huge challenges because of low quantum efficiency. Herein, we report that the solar energy conversion efficiency of Au/TiO2 in plasmon-induced water oxidation is greatly enhanced by intercalating Li+ into TiO2 . An incident photon-to-current efficiency as high as 2.0 %@520 nm is achieved by Au/Li0.2 TiO2 in photoelectrocatalytic water oxidation, realizing a 33-fold enhancement in photocurrent density compared with Au/TiO2 . The superior photoelectrocatalytic performance is mainly ascribed to the enhanced electric conductivity and higher catalytic activity of Li0.2 TiO2 . Furthermore, the ultrafast transient absorption spectroscopy suggests that lithium intercalation into TiO2 could change the dynamics of hot electron relaxation in Au nanoparticles. This work demonstrates that intercalation of alkaline ions into semiconductors can promote the charge separation efficiency of the plasmonic effect of Au/TiO2 .

Unassisted Photoelectrochemical Cell with Multimediator Modulation for Solar Water Splitting Exceeding 4% Solar-to-Hydrogen Efficiency.

Photoelectrochemical overall water splitting has been considered as a promising approach for producing chemical energy from solar energy. Although many photoelectrochemical cells have been developed for overall water splitting by coupling two semiconductor photoelectrodes, inefficient charge transfer between the light-harvesters and electron acceptor/donor severely restricts the solar energy conversion efficiency. Inspired by natural photosynthesis, we assembled a photoelectrochemical platform with multimediator modulation to achieve unassisted overall water splitting. Photogenerated electrons are transferred in order through multimediators driven by the electrochemical potential gradient, resulting in efficient charge separation and transportation with enhanced charge transfer rate and reduced charge recombination rate. The integrated system composed of inorganic oxide-based photoanode (BiVO4) and organic polymer-based photocathode (PBDB-T:ITIC:PC71BM) with complementary light absorption, exhibits a solar-to-hydrogen conversion efficiency as high as 4.3%. This work makes a rational design possible by constructing an efficient charge-transfer chain in artificial photosynthesis systems for solar fuel production.

Highly Efficient Degradation of Persistent Pollutants with 3D Nanocone TiO2-Based Photoelectrocatalysis.

Photoelectrocatalytic (PEC) degradation of organic pollutants into CO2 and H2O is a promising strategy for addressing ever-growing environmental problems. Titanium dioxide (TiO2) has been widely studied because of its good performance and environmental benignancy; however, the PEC activity of TiO2 catalyst is substantially limited due to its fast electron-hole recombination. Herein, we report a TiO2 nanocone-based photoelectrocatalyst with superior degradation performance and outstanding durability. The unique conical catalyst can boost the PEC degradation of 4-chlorophenol (4-CP) with 99% degradation efficiency and higher than 55% mineralization efficiency at a concentration of 20 ppm. The normalized apparent rate constant of a nanocone catalyst is 5.05 h-1 g-1 m2, which is 3 times that of a nanorod catalyst and 6 times that of an aggregated particle catalyst, respectively. Further characterizations reveal that the conical morphology of TiO2 can make photogenerated charges separate and transfer more efficiently, resulting in outstanding PEC activity. Moreover, computational fluid dynamics simulations indicate that a three-dimensional conical structure is beneficial for mass transfer. This work highlights that tuning the morphology of a photoelectrocatalyst at the nanometer scale not only promotes the charge transfer but also facilitates the mass transportation, which jointly enhance the PEC performance in the degradation of persistent pollutants.

Unveiling the Hydration Structure of Ferrihydrite for Hole Storage in Photoelectrochemical Water Oxidation.

Ferrihydrite (Fh) has been demonstrated acting as a hole-storage layer (HSL) in photoelectrocatalysis system. However, the intrinsic structure responsible for the hole storage function for Fh remains unclear. Herein, by dehydrating the Fh via a careful calcination, the essential relation between the HSL function and the structure evolution of Fh material is unraveled. The irreversible and gradual loss of crystal water molecules in Fh leads to the weakening of the HSL function, accompanied with the arrangement of inner structure units. A structure evolution of the dehydration process is proposed and the primary active structure of Fh for HSL is identified as the [FeO6 ] polyhedral units bonding with two or three molecules of crystal water. With the successive loss of chemical crystal water, the coordination symmetry of [FeO6 ] hydration units undergoes mutation and a more ordered structure is formed, causing the difficulty for accepting photogenerated holes as a consequence.

Tuning the Optoelectronic Property of All-Inorganic Lead-Free Perovskite via Finely Microstructural Modulation for Photovoltaics.

Bismuth-based halide perovskite materials have attracted extensive attention for optoelectronic applications due to nontoxicity and ambient stability. However, limited by low-dimensional structure and isolate octahedron arrangement, the undesirable photophysical properties of bismuth-based perovskites are still not well modulated. Here, the rational design and synthesis of Cs3 SbBiI9 with improved optoelectronic performance via premeditatedly incorporating antimony atoms with a similar electronic structure to bismuth into the host lattice of Cs3 Bi2 I9 is reported. Compared with Cs3 Bi2 I9 , the absorption spectrum of Cs3 SbBiI9 is broadened from ≈640 to ≈700 nm, the photoluminescence intensity enhances by two orders of magnitude indicating the extremely suppressed carrier nonradiative recombination, and the charge carrier lifetime is further increased from 1.3 to 207.6 ns. Taking representative applications in perovskite solar cells, the Cs3 SbBiI9 exhibits a higher photovoltaic performance benefiting from the improved intrinsic optoelectronic properties. Further structure analysis reveals that the introduced Sb atoms regulate the interlayer spacing between dimers in c-axis direction and the micro-octahedral configuration, which correlate well with the improvement of optoelectronic properties of Cs3 SbBiI9 . It is anticipated that this work will benefit the design and fabrication of lead-free perovskite semiconductors for optoelectronic applications.

Phase-Stabilized Nickel-Molybdenum Electrocatalyst by Samarium Doping for Hydrogen Evolution in Alkaline Water Electrolysis.

Although the nickel-molybdenum electrocatalyst exhibits excellent activity in the alkaline hydrogen evolution reaction (HER), its stability is poor mainly due to molybdenum leaching. This work reports that doping samarium into nickel-molybdenum electrocatalyst effectively suppresses molybdenum leaching by forming a stable phase consisting of Sm, Mo, and O elements. The resulting electrode displays no noticeable activity degradation during the long-term testing (> 850 h) under a current density of 500 mA cm-2 in 1 м KOH. This enhanced stability is ascribed to the formation of a robust phase within the HER potential windows in alkaline electrolytes, as evidenced by the Pourbaix diagram. Furthermore, the samarium-modified electrocatalyst exhibits increased activity, with the overpotential decreasing by ≈59 mV from 159 to 100 mV at 500 mA cm-2 compared to the unmodified counterpart. These remarkable properties stem from samarium doping, which not only facilitates the formation of a stable phase to inhibit molybdenum leaching but also adjusts the electronic properties of molybdenum to enhance water dissociation.

Modulating crystal facets of photoanodes for photoelectrocatalytic scalable degradation of fluorinated pharmaceuticals in wastewater.

Fluorinated pharmaceuticals pollution has become an ever-increasing environmental concern due to its negative impacts. Photoelectrocatalytic (PEC) degradation system is a desirable approach to tackle the pollution problems. However, photogenerated charge separation and interfacial mass transfer are the main bottlenecks for improving the PEC degradation performance. Herein, we report a TiO2 photoanode with tuned (101)/(110) facets in situ grown on a Ti mesh substrate for PEC degradation of fluorinated pharmaceuticals. The exposure of (101) facets facilitates efficient photogenerated charge separation and the desorption of generated •OH radical. Besides, the three-dimensional (3D) architecture of photoanode promotes macroscopic mass transfer. This system performed complete defluorination of 5-fluorouracil and more than 75 % total organic carbon (TOC) removal efficiency. The apparent reaction rate constant of high (101) facet-exposed TiO2 grown on Ti mesh is up to 6.96 h-1, 6‒fold faster than that of photoanode with low (101) facet-exposed TiO2 grown on Ti foil. It is demonstrated that a large-sized PEC system of 1200 cm2 can degrade 100 L of synthetic fluorinated pharmaceutical wastewater with more than 80 % elimination efficiency. This work showcases the facet and substrate modulated strategy of fabricating high-performed photoanode for PEC wastewater purification.

Promoting C-C coupling for CO2 reduction on Cu2O electrocatalysts with atomically dispersed Rh atoms.

Cu2O doped with atomically dispersed Rh (Rh:Cu2O) is synthesized with a wet chemical method. It shows higher activity and faradaic efficiency at lower overpotential for reduction of CO2 to C2+ products, especially C2H4, than pristine Cu2O. We found that introducing Rh promotes CO2 adsorption, *CO hydrogenation to *CHO and their coupling to O*CCHO intermediates, which contributes to enhanced catalytic performance.